Polymeric flame retardant

Abstract

The invention relates to a polymer composition containing i) styrene polymer(s) and ii) phosphorylated polyether(s) with from 0.5 to 40% by weight phosphorus content, the main chain of which is formed exclusively from carbon atoms and from oxygen atoms, and which has at least three terminal and/or pendant OH groups, where these have been substituted with where ˜ indicates the bond to the polymer skeleton of the polyether; Y is O or S; t is 0 or 1; R 1 and R 2 , being identical or different, are H, C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 2 -C 18 -alkynyl, C 3 -C 10 -cycloalkyl, C 6 -C 10 -aryl, furyl, C 6 -C 10 -aryl-C 1 -C 10 -alkyl, OR 3 , SR 3 , NR 3 R 4 , COR 3 , COOR 3 or CONR 3 R 4 , or R 1 and R 2 form, together with the phosphorus atom P, a 4-8-membered ring system; R 3 and R 4 , being identical or different, are H, C 1 -C 16 -alkyl, C 2 -C 16 -alkenyl, C 3 C 16 -alkynyl, C 3 -C 10 -cycloalkyl, C 6 -C 10 -aryl or C 6 -C 10 -aryl-C 1 -C 10 -alkyl, and/or polycarbonates containing phosphorus-containing group(s) of the general formula (I).

1 - 27 . (canceled) 
     
     
         28 . A polymer composition comprising
 i) one or more styrene polymers and   ii) one or more phosphorylated polyethers (ii-1) with from 0.5 to 40% by weight phosphorus content, the main chain of which is formed exclusively from carbon atoms and from oxygen atoms, and which has at least three terminal and/or pendant OH groups, where these have been substituted to some extent or   entirely with at least one phosphorus-containing group (I),   
       
         
           
           
               
               
           
         
         where the definitions of the symbols and indices are as follows: 
         ˜ indicates the bond to the polymer skeleton of the polyether; 
         Y is 0 or S; 
         t is 0 or 1; 
         R 1  and R 2 , being identical or different, are H, C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 2 -C 18 -alkynyl, C 3 -C 10 -cycloalkyl, C 6 -C 10 -aryl, furyl, C 6 -C 10 -aryl-C 1 -C 10 -alkyl, OR 3 , SR 3 , NR 3 R 4 , COR 3 , COORS or CONR 3 R 4 , or R 1  and R 2  form, together with the phosphorus atom P, a 4-8-membered ring system; 
         R 3  and R 4 , being identical or different, are H, C 2 -C 16 -alkenyl, C 3 -C 16 -alkynyl, C 3 -C 10 -cycloalkyl, C 6 -C 10 -aryl, furyl, C 6 -C 10 -aryl-C 1 -C 10 -alkyl 
         where aryl groups in the moieties R 1 , R 2 , R 3 , and R 4  are unsubstituted or have substitution by from 1 to 3 C 1 -C 4 -alkyl and/or C 1 -C 4 -alkoxy groups, 
         and/or 
         polycarbonates (ii-2) comprising one or more phosphorus-containing groups, where the phosphorus-containing group is a group of the general formula (I). 
       
     
     
         29 . The polymer composition according to  claim 28 , wherein
 Y is 0 or S;   t is 0 or 1;   R 1  and R 2 , being identical or different, are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 3 -C 10 -cycloalkyl, C 6 -C 10 -aryl, furyl or OR 3 ,   R 3  and R 4 , being identical or different, are C 1 -C 18 -alkyl, C 3 -C 10 -cycloalkyl or C 6 -C 10 -aryl, where aryl groups in the moieties R 1 , R 2 , R 3  and R 4  are unsubstituted or have substitution by from 1 to 3 C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy groups.   
     
     
         30 . The polymer composition according to  claim 28 , wherein
 Y is 0;   t is 0 or 1;   R 1  and R 2  are identical and are C 1 -C6-alkyl, cyclohexyl, phenyl, furyl, or OR 3 ;   R 3  is C 1 -C 6 -alkyl, cyclohexyl, or phenyl,   wherein phenyl moieties R 1 , R 2 , and R 3  are unsubstituted or have substitution by C 1 -C 4 -alkyl and/or C 1 -C 4 -alkoxy.   
     
     
         31 . The polymer composition according to  claim 28 , wherein
 Y is 0;   t is 1;   R 1  and R 2  are identical and are phenyl, phenoxy, methoxyphenyl, tolyl, furyl, cyclohexyl, methoxy, or ethoxy.   
     
     
         32 . The polymer composition according to  claim 28 , wherein the group of the formula (I) is (Ph) 2 (0)P˜ or (PhO) 2 (0)P˜ and wherein Ph is phenyl. 
     
     
         33 . The polymer composition according to  claim 28 , comprising the polyether (ii-1), wherein the polyether is hyperbranched. 
     
     
         34 . The polymer composition according to  claim 28 , comprising the polyether (ii-1) obtainable via reaction of at least one at least trihydric alcohol and optionally further di- and/or monohydric alcohols and/or modifier reagents. 
     
     
         35 . The polymer composition according to  claim 28 , comprising the polyether (ii-1) obtainable from triethylene glycol and pentaerythritol. 
     
     
         36 . The polymer composition according to  claim 35 , wherein the polyether (ii-1) is obtainable from a triethylene glycol/pentaerythritol mixture with a molar ratio in the range from 1:10 to 10:1. 
     
     
         37 . The polymer composition according to  claim 28 , comprising the polyether (ii-1) which has a number-average molar mass in the range from 100 g/mol to 50 000 g/mol. 
     
     
         38 . The polymer composition according to  claim 28 , comprising the polycarbonate (ii-2) which is hyperbranched. 
     
     
         39 . The polymer composition according to  claim 28 , comprising the polycarbonate (ii-2) which comprises no free OH groups. 
     
     
         40 . The polymer composition according to  claim 28 , comprising the polycarbonate (ii-2) which has an average OH functionality of at least two. 
     
     
         41 . The polymer composition according to  claim 28 , comprising the polycarbonate (ii-2) which has an OH number of from 2 to 800 mg KOH/g. 
     
     
         42 . The polymer composition according to  claim 28 , comprising the polycarbonate (ii-2) which comprises propylene oxide units and/or comprises ethylene oxide units. 
     
     
         43 . The polymer composition according to  claim 28 , wherein components (i) and (ii) are comprised in a mixture with one or more other flame-retardant compounds and/or with one or more synergists. 
     
     
         44 . The polymer composition according to  claim 43 , wherein the synergist is comprised of organic peroxides, organic polysulfides, C—C-cleaving initiators, or elemental sulfur. 
     
     
         45 . The polymer composition according to  claim 43 , wherein at least one sulfur compound of the formula (II) is comprised as the synergist,
   A 1 -(Z 1 )-(S) n -(Z 2 ) p -A 2   (II)
   wherein   A 1  and A 2 , being identical or different, are C 6 -C 12 -aryl, cyclohexyl, Si(OR a ) 3 , a saturated, to some extent unsaturated, or aromatic, mono- or bicyclic ring system which has from 3 to 12 ring members and which comprises one or more heteroatoms selected from the group consisting of N, O, and S, and which is unsubstituted or has substitution by one or more substituents selected from the group consisting of O, OH, S, SH, NH 2 , COOR b , CONR c R d , C 1 -C 18 -alkyl, C 1 -C 18 -alkoxy, C 1 -C 18 -thioalkyl, C 6 -C 12 -aryl, C 6 -C 12 -aryloxy, C 2 -C 18 -alkenyl, C 2 -C 18 -alkenoxy, C 2 -C 18 -alkynyl, and C 2 -C 18 -alkynoxy;   Z 1 , and Z 2  being identical or different, are —CO— or —CS—;   R a  is C 1 -C 18 -alkyl;   R b , R c , and R d , being identical or different, are H, C 1 -C 18 -alkyl, C 6 -C 12 -aryl or an aromatic, mono- or bicyclic ring system which has from 3 to 12 ring members and which comprises one or more heteroatoms selected from the group consisting of N, O, and S;   m and p, being identical or different, are 0 or 1, and   n is a natural number from 2 to 10,   and/or at least one sulfur compound of the formula (III) is comprised,   
       
         
           
           
               
               
           
         
         where the definitions of the symbols and indices are as follows: 
         R, being identical or different, is C 6 -C 12 -aryl, a 5-10-membered heteroaryl group which comprises one or more heteroatoms from the group of N, O, and S, C 1 -C 16 -alkyl, C 2 -C 18 -alkenyl, C 3 -C 16 -alkynyl, or C 3 -C 10 -cycloalkyl; 
         X, being identical or different, is OR y , SW y , NR Y R Z , COOR y , CONR y , SO 2 R y , F, Cl, Br, R, H, or a group —Y 1 —P(Y 2 ) p R′R″; 
         Y 1  is 0, S, or NR″′; 
         Y 2  IS 0 or S; 
         p is 0 or 1; 
         R′ and R″, being identical or different, are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 3 -C 18 -alkynyl, C 6 -C 12 -aryl, C 3 -C 10 -cycloalkyl, C 6 -0 12 -aryl-C 1 -C 18 -alkyl, or a heteroaryl group or heteroaryloxy group which comprises one or more heteroatoms selected from the group consisting of N, O, and S, O—(C 1 -C 18 )-alkyl, O—(C 2 -C 18 )-alkenyl, O—(C 3 -C 10 )-alkynyl, O—(C 6 -0 12 )-aryl, O—(C 3 -C 10 )-cycloalkyl or O—(C 6 -C 12 )-aryl-(C 1 -C 18 )-alkyl; 
         R″′ is H, C 1 -C 18 -alkyl or (P(Y 2 ) p R′R″); 
         R x , being identical or different, is C 1 -C 18 -alkyl, C 2 -C 10 -alkenyl, C 3 -C 10 -alkynyl, C 6 -C 12 -aryl, C 3 -C 10 -cycloalkyl, C 6 -C 12 -aryl-C 1 -C 18 -alkyl, a heteroaryl group which comprises one or more heteroatoms selected from the group consisting of N, O, and S, 
         C 1 -C 18 -alkyl, C 2 -C 16 -alkenyl, C 3 -C 18 -alkynyl or C 3 -C 10 -cycloalkyl, O—(C 1 -C 18 )-alkenyl, O—(C 3 -C 10 )-alkynyl, O—(C 6 -C 12 )-aryl, O—(C 3 -C 10 )-cycloalkyl, O—(C 6 -C 12 )-aryl-(C 1 -C 18 )-alkyl, S—(C 1 -C 18 )-alkyl, S—(C 1 -C 18 )-alkenyl, S—(C 3 -C 10 )-alkynyl, S—(C 6 -C 12 )-aryl, S—(C 3 -C 10 )-cycloalkyl, (C 6 -C 12 )-aryl-(C 1 -C 18 )-alkyl-S, Fl, Cl, Br or H; 
         R y  and R z  being identical or different, are H, C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 3 -C 18 -alkynyl, C 6 -C 12 -aryl, C 3 -C 10 -cycloalkyl, C 6 -C 12 -aryl-C 1 -C 18 -alkyl, or a heteroaryl group which comprises one or more heteroatoms from the group of N, O, and S, 
         n is an integer from 1 to 8, and 
         m is a number from 1 to 1000. 
       
     
     
         46 . The polymer composition according to  claim 28 , in the form of an expandable styrene polymer (EPS). 
     
     
         47 . The polymer composition according to 28, in the form of an extruded styrene polymer foam (XPS). 
     
     
         48 . A process for producing the expandable styrene polymer (EPS) according to  claim 46 , comprising the following steps:
 a) mixing to incorporate an organic blowing agent and a flame retardant (ii) and optionally further auxiliaries and additives into a styrene polymer melt by means of static and/or dynamic mixers at a temperature of at least 150° C.,   b) cooling of the styrene polymer melt comprising blowing agent to a temperature of at least 120° C.,   c) discharging through a die plate with holes, the diameter of which at the die outlet is at most 1.5 mm, and   d) pelletizing the melt comprising blowing agent directly behind the die plate under water at a pressure in the range from 1 to 20 bar.   
     
     
         49 . A process for producing the expandable styrene polymer according to  claim 46 , comprising the following steps:
 a) polymerizing one or more styrene monomers in suspension;   b) adding a flame retardant (ii) and also optionally of her auxiliaries and additives prior to, during and/or after the polymerization reaction;   c) adding an organic blowing agent prior to, during, and/or after the polymerization reaction, and   d) isolating, from the suspension, the expandable styrene polymer particles comprising the flame retardant.   
     
     
         50 . A process for producing the extruded styrene foam (XPS) according to  claim 47 , comprising the following steps:
 a) heating a polymer component P which comprises at least one styrene polymer, to form a polymer melt,   b) introducing a blowing agent component T into the polymer melt to form a foamable melt,   c) extruding the foamable melt into a region of relatively low pressure with foaming to give an extruded foam, and   d) adding a flame retardant (ii) and also optionally of further auxiliaries and additives in at least one of steps a) and b).   
     
     
         51 . An insulation material comprising the polymer composition according to  claim 47 . 
     
     
         52 . An insulation material comprising the polymer composition according to  claim 46  in expanded form. 
     
     
         53 . A phosphorylated polyether (ii-1) with from 0.5 to 40% by weight phosphorus content, the main chain of which is formed exclusively from carbon atoms and from oxygen atoms, and which has at least three terminal and/or pendant OH groups, where these have been substituted to some extent or
 entirely with at least one phosphorus-containing group (I),   
       
         
           
           
               
               
           
         
         where the definitions of the symbols and indices are as follows: 
         ˜ indicates the bond to the polymer skeleton of the polyether; 
         Y is 0 or S; 
         t is 0 or 1; 
         R 1  and R 2 , being identical or different, are H, C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 2 -C 18 -alkynyl, C 3 -C 10 -cycloalkyl, C 6 -C 10 -aryl, furyl, C 6 -C 10 -aryl-C 1 -C 10 -alkyl, OR 3 , SR 3 , NR 3 R 4 , COR 3 , COORS or CONR 3 R 4 , or R 1  and R 2  form, together with the phosphorus atom P, a 4-8-membered ring system; 
         R 3  and R 4 , being identical or different, are H, C 1 -C 16 -alkyl, C 2 -C 16 -alkenyl, C 3 -C 16 -alkynyl, C 3 -C 10 -cycloalkyl, C 6 -C 10 -aryl, furyl, C 6 -C 10 -aryl-C 1 -0 10 -alkyl and 
         wherein aryl groups in the moieties R 1 , R 2 , R 3 , and R 4  are unsubstituted or have substitution by from 1 to 3 C 1 -C 4 -alkyl and/or C 1 -C 4 -alkoxy groups. 
       
     
     
         54 . A process for producing the phosphorylated polyether (ii-1) according to  claim 53 , comprising reacting a polyether, the main chain of which is formed exclusively from carbon and oxygen atoms, and which comprises at least three terminal and/or pendant OH groups, with a phosphorus compound (I-A), 
       
         
           
           
               
               
           
         
         wherein X is Cl, Br, I, (C 1 -C4)-alkoxy, or H, and the definitions of the remaining symbols are those stated in formula (I), so that the reaction product has from 0.5 to 40% by weight phosphorus content. 
       
     
     
         55 . A flame retardant, comprising the phosphorylated polyether according to  claim 52 .